CN110467529B - Synthesis method of ester - Google Patents
Synthesis method of ester Download PDFInfo
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- CN110467529B CN110467529B CN201910646191.1A CN201910646191A CN110467529B CN 110467529 B CN110467529 B CN 110467529B CN 201910646191 A CN201910646191 A CN 201910646191A CN 110467529 B CN110467529 B CN 110467529B
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- quaternary ammonium
- ammonium salt
- fluoride
- alcohol
- carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic chemical synthesis, and discloses a synthesis method of ester, which specifically comprises the following steps: the ester is synthesized by the dehydration reaction between carboxylic acid and alcohol promoted by common imidazole quaternary ammonium salt, thiazole quaternary ammonium salt or triazole quaternary ammonium salt and fluoride. The method has the advantages of cheap raw materials, simple and convenient process, greenness, safety, high efficiency and environmental protection, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, relates to a synthesis method of ester, and particularly relates to a method for synthesizing ester by dehydration reaction between carboxylic acid and alcohol promoted by common imidazole quaternary ammonium salt, thiazole quaternary ammonium salt or triazole quaternary ammonium salt and fluoride.
Background
The reaction of carboxylic acid and alcohol dehydration to synthesize ester is the most basic and important organic reaction, and is widely applied to drug synthesis, material chemistry and life chemistry. At present, the main method for constructing ester is high-temperature dehydration under strong acidic condition, which has low efficiency for complex substrate and brings many byproducts. Another method is to use condensing agents such as combinations of triphenylphosphine and DMAP, which tend to be less active, and require large amounts of auxiliary reagents.
Disclosure of Invention
The invention aims to provide a synthesis method of ester, which comprises the following specific steps:
in an organic solvent, carboxylic acid and alcohol are used as raw materials, imidazole quaternary ammonium salt, thiazole quaternary ammonium salt or triazole quaternary ammonium salt and fluoride are used as promoters, ester is prepared by dehydration reaction in the presence of an oxidant, and meanwhile, degradation products of the imidazole, thiazole or triazole quaternary ammonium salt can be recovered and reused by reduction.
The carboxylic acid is a compound containing a carboxyl functional group (-COOH) and is aliphatic carboxylic acid or aryl carboxylic acid.
The alcohol is a compound containing hydroxyl functional groups (-OH), and is aliphatic alcohol or phenol.
The chemical structural formula of the quaternary ammonium salt of the imidazole, the thiazole or the triazole is respectively as follows:
wherein R is1，R2，R3，R4Is alkyl, aryl or heterocyclic radical. The imidazole quaternary ammonium salt is shown in a structure (1), the thiazole quaternary ammonium salt is shown in a structure (2), and the triazole quaternary ammonium salt is shown in a structure (3).
The fluoride is a fluorine-containing salt, such as potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride or ammonium fluoride.
The oxidant used in the reaction is potassium persulfate, sodium persulfate, tert-butyl peroxide, oxone or oxygen.
The organic solvent used in the reaction is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, toluene, tetrahydrofuran, tert-butyl methyl ether, diethyl ether, acetonitrile, acetone, dimethyl sulfoxide or N, N-dimethylformamide.
The mass ratio of the carboxylic acid to the alcohol is 1: 1; the mass ratio of the oxidant to the alcohol is 1.0: 1.0-2.0: 1.0; the mass ratio of the fluoride to the alcohol is 1.0: 1.0 to 2.0: 1.0.
The quantity ratio of the imidazole quaternary ammonium salt, the thiazole quaternary ammonium salt or the triazole quaternary ammonium salt to the fluoride is 1: 1.
The invention has the beneficial effects that:
(1) the synthesis method of the ester compound provided by the invention has the advantages of cheap raw materials, simple and convenient process and easy industrial preparation.
(2) The dehydration reaction between carboxylic acid and alcohol promoted by common quaternary ammonium salt of imidazole, thiazole or triazole and fluoride provided by the invention can efficiently synthesize ester compounds, and the method is green, safe, efficient and environment-friendly, and is suitable for industrial production.
Detailed Description
The first embodiment is as follows:
a500 ml reaction flask was charged with 200ml of t-butyl methyl ether as a solvent, 12.2 g (0.1mol) of benzoic acid, 13.3 g (0.1mol) of 1, 4-dimethyltriazole chloride, 5.8 g (0.1mol) of potassium fluoride, 7.4 g (0.1mol) of n-butanol, and 24 g (0.1mol) of sodium persulfate in this order, reacted at room temperature for 27 hours, and then extracted with water and ethyl acetate three times to remove the water layer, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporator and purified by silica gel chromatography (ethyl acetate/petroleum ether-1/10) to give pure n-butyl benzoate 16 g in 90% yield.
Example two:
a500 ml reaction flask was charged with 200ml of t-butyl methyl ether as a solvent, 7.4 g (0.1mol) of propionic acid, 13.3 g (0.1mol) of 1, 4-dimethyltriazole chloride, 5.8 g (0.1mol) of potassium fluoride, 9.4 g (0.1mol) of phenol, and 24 g (0.1mol) of sodium persulfate in this order, reacted at room temperature for 27 hours, and then extracted with water and ethyl acetate three times to remove the water layer, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporator and purified by silica gel chromatography (ethyl acetate/petroleum ether-1/10) to give pure phenyl propionate 12 g with 80% yield.
Claims (6)
1. A method for synthesizing an ester, comprising the steps of: in an organic solvent, carboxylic acid and alcohol are used as raw materials, imidazole quaternary ammonium salt, thiazole quaternary ammonium salt or triazole quaternary ammonium salt and fluoride are used as promoters, and ester is prepared by dehydration reaction in the presence of an oxidant;
the fluoride is potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride or ammonium fluoride;
the chemical structural formulas of the imidazole quaternary ammonium salt, the thiazole quaternary ammonium salt or the triazole quaternary ammonium salt are respectively as follows:
wherein R is1，R2，R3，R4Is alkyl, aryl or heterocyclic radical.
2. The method for synthesizing esters according to claim 1, wherein the carboxylic acid is a compound having a carboxyl functional group (-COOH), and the alcohol is a compound having a hydroxyl functional group (-OH).
3. The method of claim 2, wherein the carboxylic acid is an aliphatic or aromatic carboxylic acid and the alcohol is an aliphatic or phenolic alcohol.
4. The method for synthesizing ester according to claim 1, wherein the oxidizing agent used in the reaction is potassium persulfate, sodium persulfate, t-butanol peroxide, oxone complex salt or oxygen.
5. The method for synthesizing ester according to claim 1, wherein the organic solvent used in the reaction is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, toluene, tetrahydrofuran, tert-butyl methyl ether, diethyl ether, acetonitrile, acetone, dimethyl sulfoxide or N, N-dimethylformamide.
6. The method of synthesizing esters according to claim 1, wherein the mass ratio of the carboxylic acid and alcohol is 1: 1; the mass ratio of the oxidant to the alcohol is 1.0: 1.0-2.0: 1.0; the mass ratio of the fluoride to the alcohol is 1.0: 1.0-2.0: 1.0, and the mass ratio of the imidazole quaternary ammonium salt, the thiazole quaternary ammonium salt or the triazole quaternary ammonium salt to the fluoride is 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910646191.1A CN110467529B (en) | 2019-07-17 | 2019-07-17 | Synthesis method of ester |
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| CN201910646191.1A CN110467529B (en) | 2019-07-17 | 2019-07-17 | Synthesis method of ester |
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| CN110467529A CN110467529A (en) | 2019-11-19 |
| CN110467529B true CN110467529B (en) | 2021-11-23 |
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| CN201910646191.1A Active CN110467529B (en) | 2019-07-17 | 2019-07-17 | Synthesis method of ester |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304392A (en) * | 1999-03-08 | 2001-07-18 | 株式会社德山 | Process for producing carboxylic acid derivative and condensing agent comprising quaternary ammonium salt |
| JP2013056879A (en) * | 2011-06-20 | 2013-03-28 | Sumitomo Chemical Co Ltd | Process for producing carboxylic acid ester |
| CN109400476A (en) * | 2018-12-06 | 2019-03-01 | 华东理工大学 | A kind of preparation method of long-chain ester |
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2019
- 2019-07-17 CN CN201910646191.1A patent/CN110467529B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304392A (en) * | 1999-03-08 | 2001-07-18 | 株式会社德山 | Process for producing carboxylic acid derivative and condensing agent comprising quaternary ammonium salt |
| JP2013056879A (en) * | 2011-06-20 | 2013-03-28 | Sumitomo Chemical Co Ltd | Process for producing carboxylic acid ester |
| CN109400476A (en) * | 2018-12-06 | 2019-03-01 | 华东理工大学 | A kind of preparation method of long-chain ester |
Non-Patent Citations (1)
| Title |
|---|
| 酯化方法及催化酯化中催化剂应用的研究进展;王连福;《天津药学》;20141231;第26卷(第6期);64-66 * |
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Effective date of registration: 20211011 Address after: 332000 Xinghuo Industrial Park, Yongxiu Yunshan Economic Development Zone, Yongxiu County, Jiujiang City, Jiangxi Province Applicant after: Jiangxi Maihao Chemical Technology Co., Ltd Address before: 212013 No. 301 Xuefu Road, Jingkou District, Zhenjiang City, Jiangsu Province Applicant before: jiangsu university |
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